Linear amine functionalized poly(trimethylene ether) compositions

ABSTRACT

The present invention relates to linear amine-functionalized poly(trimethylene ether) compositions, and processes to produce these compositions.

FIELD OF THE INVENTION

The present invention relates to linear amine-functionalizedpoly(trimethylene ether) compositions, and processes for producing thecompositions.

BACKGROUND

Poly(trimethylene ether)glycol is widely used as an intermediate inthermoplastic elastomers. Processes for preparing polyoxyalkylenepolyamines using polyoxyalkylene glycols with ammonia and hydrogen inthe presence of Raney nickel catalysts are disclosed in U.S. Pat. No.3,236,895. Poly(ethylene glycol) derivatives also reported by J. MiltonHarris (J. Macromolecular Science Reviews in Macromolecular Chemistry,1985, vol C-25, No. 3, P325-373).

Poly(trimethylene ether)amines are useful in a variety of applicationssuch as chain extenders for polyurethane urea polymers, curing agentsfor epoxy resins, polyurethane coatings, components for makingpolyamides, initiators for the preparation of polyols, or health careproduct additives.

SUMMARY OF THE INVENTION

One aspect of the present invention is a poly(trimethylene ether)diaminecompound of the formula

wherein n is 4 to 170, preferably 4 to 100.

Another aspect of the present invention is a process for making apoly(trimethylene ether)diamine of the formula

wherein n is 4 to 170, preferably 4 to 100, comprising:a) contacting poly(trimethylene ether)glycol of the formula

with thionyl halide and optionally with dimethylformamide, optionally inthe presence of a solvent, at a temperature less than about 25° C., toform a reaction mixture;b) raising the temperature of the reaction mixture to a temperature of50 to 150° C. and holding the reaction mixture at the raised temperaturefor about 2 to 24 hours;c) allowing the formation of a poly(trimethylene ether)halide of theformula

wherein X is Cl or Br;d) combining the poly(trimethylene ether)halide with 1-10 molarequivalents of alkali metal azide in the presence of a solvent at atemperature of 25 to 200° C. to form a poly(trimethylene ether)azide ofthe formula

ande) contacting the poly(trimethylene ether)azide with a reducing agent,or under hydrogen gas with catalytic amount of catalyst, in a solvent orsolvent mixture, at a pressure of about 15 to 500 psi and at atemperature of 25 to 200° C., to form a poly(trimethylene ether)amine ofthe structure

wherein n is 4 to 170, preferably 4 to 100.

A further aspect of the present invention is a process for making apoly(trimethylene ether)diamine of the formula

comprising:a) providing a poly(trimethylene ether)glycol, having chain-end hydroxylgroups, of the formula

and converting the chain-end hydroxyl groups of the poly(trimethyleneether)glycol to form a compound of formula

where Z is selected from the group consisting of: mesylate (—OMs),tosylate (—OTs), nosylate (—ONs), brosylate (—OBs), triflate (—OTf),nonaflate, tresylate, iodide (—I)b) combining the compound from step (a) with 1-10 molar equivalents ofalkali metal azide in the presence of a solvent at a temperature of 25to 200° C. to form a poly(trimethylene ether)azide of the formula

andc) contacting the poly(trimethylene ether)azide with a reducing agentor, under hydrogen gas with catalytic amount of catalyst, in a solventor solvent mixture, at a pressure of about 15 to 500 psi and at atemperature of 25 to 200° C., to form a poly(trimethylene ether)amine ofthe structure

wherein n is 4 to 170, preferably 4 to 100.

Another aspect of the present invention is a process for making apoly(trimethylene ether)diamine of the formula

comprising:a) contacting poly(trimethylene ether)glycol of the formula

with thionyl halide and optionally with catalytic amount ofdimethylformamide (DMF), optionally in the presence of a solvent, at atemperature less than about 25° C. to form a reaction mixture;b) raising the temperature of the reaction mixture to a temperature of50 to 150° C., and holding the reaction mixture at the raisedtemperature for about 2 to 24 hours to form a poly(trimethyleneether)halide of the formula:

wherein X is Cl or Br;c) contacting the poly(trimethylene ether)halide with anhydrous ammonia,or a mixture of aqueous ammonia and a suitable solvent, under a pressureof 15 to 500 psi and at a temperature of 25 to 150° C. to form apoly(trimethylene ether)diamine of the formula

wherein n is 4 to 170, preferably 4 to 100.A further aspect of the present invention is a process for making apoly(trimethylene ether)diamine of the formula

comprising:a) converting poly(trimethylene ether)glycol of the formula

to a compound of formula

where Z is selected from the group consisting of mesylate (—OMs),tosylate (—OTs), nosylate (—ONs), brosylate (—OBs), triflate (—OTf),nonaflate, tresylate and iodide (—I);b) combining the compound from step (a) with anhydrous ammonia or amixture of aqueous ammonia and a suitable solvent under a pressure ofabout 15 to 500 psi at a temperature of 25 to 150° C. to form apoly(trimethylene ether)diamine of the formula

wherein n is 4 to 170, preferably 4 to 100.

Another aspect of the present invention is a process for making apoly(trimethylene ether)diamine of the formula

comprising:a) providing a poly(trimethylene ether)glycol of the formula

and converting the chain-end hydroxyl groups thereof to form anitrile-terminated poly(trimethylene ether) of formula

b) reducing the nitrile-terminated poly(trimethylene ether) in thepresence of hydrogen and catalyst at a temperature of 50 to 250° C.under a pressure of 80 to 4000 psi to form a poly(trimethyleneether)diamine of the formula

wherein n is 4 to 170, preferably 4 to 100.

These and other aspects of the present invention will be apparent to oneskilled in the art in view of the present disclosure and the appendedclaims.

DETAILED DESCRIPTION

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In case of conflict, thepresent specification, including definitions, controls.

The present invention provides linear amine-functionalizedpoly(trimethylene ether) compositions, and processes to produce them.

Generally, the compositions made according to the processes disclosedherein are known as poly(trimethylene ether)diamines and have thestructure

wherein n is 4 to 170, and preferably 4 to 100.

Processes disclosed herein for making the poly(trimethyleneether)diamines generally begin by contacting poly(trimethyleneether)glycol having the structure

wherein n is 4 to 170, and preferably 4 to 100, with a chemical compoundthat will react with the glycol.

Unless stated otherwise, weight percentages given herein, particularlywith respect to reactants and compounds, including catalysts, that arecontacted with a poly(trimethylene ether)glycol or a compound derivedtherefrom, are relative to the weight of the poly(trimethyleneether)glycol compound or derived compound.

In one embodiment, the poly(trimethylene ether)glycol is reacted withthionyl chloride or thionyl bromide, optionally containing astoichiometric amount (up to 80% by weight), or preferably a catalyticamount (0.01% to 15% by weight, preferably 0.1% to 10% by weight) ofdimethyl formamide, neat or in the presence of a solvent that it iscompatible with poly(trimethylene ether)glycol, at controlledtemperatures, generally within the range from ⁻78° C. to roomtemperature (e.g., about 25° C.), typically from about ⁻20° C. to 10°C., more typically around 0° C.) to form a reaction mixture. Suitablecompatible solvents include toluene, dichloromethane, ethyl acetate,ethyl ether, ethanol, methanol, acetone, dioxane, tetrahydrofuranhexane, and cyclohexane. The choice of solvent depends in part on themolecular weight of the poly(trimethylene ether)glycol. Polar solventssuch as alcohols, esters, and ethers are generally preferred for lowermolecular weight polymers, and aliphatic hydrocarbon solvents such aspentane, petroleum ether and hexane are generally preferred for highermolecular weight polymers. The temperature of the reaction mixture isthen raised to a temperature of 50 to 150° C., generally 50 to 100° C.,and held at the raised temperature for about 2 to about 24 hours withstirring, and a dihalide compound is thereby formed, having thestructure

where X is Cl or Br derived from the thionyl compound with which thepoly(trimethylene ether)glycol was reacted.

The resulting poly(trimethylene ether)halide is then combined withappropriate amount of alkali metal azide such as, for example, sodiumazide to allow for the conversion of the halide functional groups toazide functional groups, in dimethylformamide solvent at an elevatedtemperature, generally 25 to 200° C., more typically 50 to 150° C.)either at atmosphere pressure or a pressure of 15 to 150 psi dependingon the choice of solvent, temperature, and catalyst to form apoly(trimethylene ether)azide of the structure

The preferred amount of alkali metal azide is 1 to 10 molar equivalentsto the halide functional groups. Other solvents, preferably polarsolvents, can be used for this reaction, such as, for example, water,acetone, methanol, isopropanol, N,N′-dimethylformamide (DMF),dimethylsulfoxide (DMSO), N,N′-dimethylacetamide (DMAc),N-methylpyrrolidone (NMP) and mixtures thereof.

The poly(trimethylene ether)azide is then exposed to a catalyst(generally 0.01% to 15% by weight, preferably 0.1% to 10% by weight) inthe presence of hydrogen gas at ambient or elevated temperature,generally 25 to 200° C., and more typically 50 to 150° C., and atambient pressure or elevated pressure, typically 15 to 500 psi,preferably 20 to 100 psi, to form the desired poly(trimethyleneether)amine. One suitable catalyst is palladium, 10 wt. % on activatedcarbon, which is available from commercial suppliers, such asSigma-Aldrich. However, a variety of catalysts can be used, includingcobalt-nickel, cobalt manganese, cobalt boride, copper cobalt, ironoxide, zinc, Raney nickel, rhodium on charcoal or alumina, rhodiumhydroxide, platinum-rhodium oxide, or platinum on carbon, etc. Reactionconditions such as, for example, choice of solvent, reaction pressureand co-catalyst, can be varied by one skilled in the art. Alternately,other reducing agents, such as, for example, triphenylphosphine, sodiumboron hydride, and lithium aluminum hydride, can be used alone toconvert the azide to the amine.

Poly(trimethylene ether)glycols have chain-end hydroxyl groups that canbe reacted and converted to other groups. In some embodiments, thechain-end hydroxyl groups of the poly(trimethylene ether)glycols areconverted to better leaving groups for nucleophilic substitutionreactions. “Better leaving groups”, as used herein, means leaving groupsthat are better than hydroxyl groups. Leaving groups in connection withnucleophilic substitution reactions are discussed in page 352-357,March's Advanced Organic Chemistry (4^(th) Edition) by Michael B. Smithand Jerry March, John Wiley and Son's Inc. Compounds having such betterleaving groups include reactive esters, oxonium ions, and fluorinatedcompounds of the following formula:

where Z is, for example: mesylate (—OMs), tosylate (—OTs), nosylate(—ONs), brosylate (—OBs), triflate (—OTf), nonaflate, tresylate, iodide(—I). Particularly preferred leaving groups include those selected fromthe group consisting of: —OMs (wherein Ms is methanesulfonyl), OTs(wherein, Ts is toluenesulfonyl), —ONs (wherein Ns isp-nitrobenzenesulfonyl), —OBs (wherein Bs is p-bromonenznesulfonyl),—OTf (wherein Tf is trifluoromethanesulfonyl), nonaflate(nonafluorobutanesulfonate), and tresylate(2,2,2,-trifluoroethanesulfonate). One embodiment of the processincludes contacting poly(trimethylene ether)glycol with halides oranhydrides of the acid comprising the better living groups such as thoserecited hereinabove, and a base, in the presence of a solvent that iscompatible with poly(trimethylene ether)glycol, such as dichloromethaneor toluene, at a temperature of 0° C. or lower (typically from about−78° C. to 0° C., and more preferably from about −20° C. to 0° C.) underan inert atmosphere, such as, for example nitrogen or argon. Suitablebases include, for example, either inorganic base such as sodiumhydroxide, potassium hydroxide, sodium (bi)carbonate, potassium(bi)carbonate, or organic base, such as trimethylamine, triethylamine,di-isopropylethylamine, and pyridine. After the reaction ofpoly(trimethylene ether)glycol with the acid halides or acid anhydridesis completed, the reaction mixture is optionally neutralized, forexample, with a dilute acid such as HCl, HOAc, H₂SO₄, HNO₃, or with anion exchange resin, then optionally filtered, and optionally furtherpurified by extraction with solvents, such as ether, dichloromethane,chloroform, ethyl acetate, to provide poly(trimethylene ether) compoundsof the following chemical structures:

Other compounds having preferred leaving groups include iodides (I) offormula

which can be prepared by further treatment of the chain-end chloride orbromide functionalized poly(trimethylene ether) compounds with an iodidesource, such as sodium iodide or potassium iodide, in the presence ofpolar solvents, such as water, acetone, methanol, isopropanol,N,N′-dimethylformamide (DMF), dimethylsulfoxide (DMSO),N,N′-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and mixturesthereof.

The abovementioned chain-end iodide functionalized poly(trimethyleneether) compound can also be synthesized by direct iodination ofpoly(trimethylene ether)glycol whereby the chain end hydroxyl groups areconverted to iodide groups. A variety of reagents can be used, such as,for example, BF₃-Et₂O/NaI, I₂, MgI₂, triphenylphosphine/iodine/ImH. asdisclosed, for example, in Hajipour et al (Tetrahedron Letters, 2006,47, 4191-4196) as well as Reference 5-18 referenced therein.

The poly(trimethylene ether) compound, comprising a better leaving groupZ, of formula

where Z is, for example: mesylate (—OMs), tosylate (—OTs), nosylate(—ONs), brosylate (—OBs), triflate (—OTf), nonaflate, tresylate, oriodide (—I) is then combined with sufficient amount of azide source toachieve the desired degree of azide functional group conversion,typically an alkali metal azide, such as sodium azide, in the presenceof a solvent (typically polar solvents and alcohol solvents) at elevatedtemperature (25 to 200° C., and more typically 50 to 150° C.) under apressure of 15 to 150 psi, or under atmospheric pressure, to formpoly(trimethylene ether)azide of the formula

The poly(trimethylene ether)azide is then exposed to a reducing agent,such as a catalyst in the presence of hydrogen gas, at elevated pressure(15 to 500 psi, typically 20 to 100 psi) and at ambient temperature,whereby the desired poly(trimethylene ether)amine is formed. Usefulreducing agents include catalysts such as metal catalysts selected fromthe group consisting of: Pt, Pd, PtO₂, Pd/C, and Raney nickel;triphenylphosphine; lithium aluminum hydride; borohydrides selected fromthe group consisting of: sodium borohydride, zinc borohydride, andlithium aminoborohydride wherein the amine is selected from the groupconsisting of diethylamine, diisopropylamine, pyrrolidine, piperidine,and morpholine; metal and metal salts selected from the group consistingof zinc and tin (II) chloride; and ammonium formate. Preferred reactionsolvents are polar aprotic solvents such as N,N-dimethylformamide orN,N-dimethylacetamide, or alcohol solvents such as methanol, ethanol,and isopropanol. The catalyst is preferably dispersed on charcoal orsilica. The catalyst and/or other remaining reducing agents aredesirably removed after the reducing step is complete.

In another embodiment, poly(trimethylene ether)glycol is reacted withthionyl halide optionally containing a catalytic amount ofdimethylformamide in the presence of a solvent to form the dihalide asdescribed above, which is then dissolved in a mixture of aqueous ammoniaand an appropriate solvent under elevated pressure (15-500 psi) and atelevated temperature (25 to 150° C., preferably 40 to 100° C.) to formthe desired poly(trimethylene ether)diamine. An appropriate solvent isone that preferably does not react with ammonia and allows for thesolubilization of poly(trimethylene ether) intermediate. Suitablesolvents include, for example, alcohol solvents, polar aprotic solvents,and toluene.

In still another embodiment, poly(trimethylene ether)glycol is reactedwith thionyl halide optionally containing a stoichiometric amount,preferably a catalytic amount, of dimethylformamide in the presence of asolvent to form the dihalide as described above, which is then exposedto anhydrous ammonia under elevated pressure (15 to 500 psi) and atelevated temperature (25 to 150° C., preferably 40-100° C.) to form thedesired poly(trimethylene ether)diamine. The solvent preferably does notreact with ammonia and allows for the solubilization ofpoly(trimethylene ether) intermediate. Suitable solvents include alcoholsolvents, polar aprotic solvents, and toluene.

In yet another embodiment, the chain end hydroxyl groups are convertedto better leaving groups. Especially preferred better leaving groupsinclude those selected from the group consisting of: —OMs (wherein Ms ismethanesulfonyl), —OTs (wherein Ts is toluenesulfonyl), —OTf (wherein Tfis trifluoromethanesulfonyl), tresylate(2,2,2,-trifluoroethanesulfonate), and —I. The product can then bedissolved in a mixture of aqueous ammonia and an appropriate solventunder elevated pressure (15-500 psi) and at ambient or elevatedtemperature (25 to 150° C., preferably 25 to 80° C.) to form the desiredpoly(trimethylene ether)diamine. The solvent preferably does not reactwith ammonia and allows for the solubilization of poly(trimethyleneether) intermediate. Suitable solvents include alcohol solvents, polaraprotic solvents, and toluene.

In still another embodiment, the product formed by the reaction of thepoly(trimethylene ether)glycol and better leaving group as describedabove is exposed to anhydrous ammonia under elevated pressure (15 to 500psi) and at elevated temperature (25 to 150° C., preferably 25 to 80°C.) to form the desired poly(trimethylene ether)diamine. The solventpreferably does not react with ammonia and allows for the solubilizationof poly(trimethylene ether) intermediate. Suitable solvents includealcohol solvents, polar aprotic solvents, and toluene.

In still another embodiment, the chain end hydroxyl groups ofpoly(trimethylene ether)glycol are converted to nitrile groups bycyanoethylation reaction to form a nitrile-terminated poly(trimethyleneether) of formula

Cyanoethylation reaction is typically performed with acrylonitrile inthe presence of catalytic amount of base, such as sodium hydroxide orpotassium hydroxide, and ppm level of radical inhibitor, such as, forexample, monomethyl ether hydriquinone (MEHQ), butylated hydroxyltoluene (BHT). A process for cyanoethylation is disclosed, for example,in Harper et al in Kirk-Othmer Encyclopedia of Chemical Technology,3^(rd) Ed, 1979, volume 7, page 370-385 as well as the references citedin Harper et al.

The nitrile terminated poly(trimethylene ether) compound is then reducedto form the amine-terminated poly(trimethylene ether) compound offormula

Typical reaction conditions for reducing nitriles to amines aredescribed in detail by de Bellefon et al in Catalysis Reviews, Scienceand Engineering, 1994, volume 36, issue 3, page 459-506 as well as thereferences cited in de Bellefon et al. Suitable solvents for thisreaction include: water, alcohol solvents (for example, methanol,ethanol, and isopropanol), ether solvents (for example, THF, dioxane),aromatic solvents (for example, benzene and toluene), hydrocarbonsolvents (for example, hexane and octane), or mixtures thereof. Avariety of catalysts can be used for this reaction includingcobalt-nickel, cobalt manganese, cobalt boride, copper cobalt, ironoxide, Raney nickel, rhodium on charcoal or alumina, rhodium hydroxide,platinum-rhodium oxide, palladium or platinum on carbon, etc. The amountof catalyst is generally 0.01% to 15% by weight, preferably 0.1% to 10%by weight. The reaction temperature is generally from 50 to 250° C.,more typically from 80 to 150° C. The reaction pressure is generallyfrom 80 to 4000 psi, more typically from 150 to 1500 psi. Additives,including base, acid, or acid anhydride, can be desirably used used tominimize the formation of secondary and tertiary amines. Examplesinclude ammonia, hydroxide, hydrogen chloride, and acetic anhydride. Thereaction conditions can be varied, such as by choice of solvent,reaction pressure and co-catalyst, by one skilled in the art.

The poly(trimethylene ether)diamines produced by the processes describedherein can be purified by any convenient method known to those skilledin the art. Particularly useful methods include washing and extractingwith solvents, passing the material through one or more ion exchangecolumns, or subjecting the diamines to dialysis against solvents usingdialysis apparatus comprising separation membranes, or treating withactivated carbon, or a combination of the above. Suitable solvents forpurification are solvents that are compatible with the poly(trimethyleneether)diamines, such as, for example, hexane, heptane, toluene, xylenes,dichloromethane, chloroform, isopropanol, ethanol, methanol, ethyleneglycol, propylene glycol, water, ether, tetrahydrofuran, dioxane,acetonitrile, acetone, ethyl acetate, N,N′-dimethylformamide (DMF),dimethylsulfoxide (DMSO), N,N′-dimethylacetamide (DMAc),N-methylpyrrolidone (NMP) and mixtures thereof.

The processes described herein use poly(trimethylene ether)glycol(PO3G), as a starting component to make the linear diamine moieties. Asthe term PO3G is used herein, it represents an oligomeric or polymericether glycol in which at least 50% of the repeating units aretrimethylene ether units. More preferably from about 75% to 100%, stillmore preferably from about 90% to 100%, and even more preferably fromabout 99% to 100%, of the repeating units are trimethylene ether units.

PO3G is preferably prepared by polycondensation of monomers comprising1,3-propanediol, preferably in the presence of an acid catalyst, thusresulting in polymers or copolymers containing —(CH₂CH₂CH₂O)— linkage(e.g, trimethylene ether repeating units). As indicated above, at least50% of the repeating units are trimethylene ether units. A preferredsource of 1,3-propanediol is via a fermentation process using arenewable biological source. As an illustrative example of a startingmaterial from a renewable source, biochemical routes to 1,3-propanediol(PDO) have been described that utilize feedstocks produced frombiological and renewable resources such as corn feed stock.

In addition to the trimethylene ether units, lesser amounts of otherunits, such as other polyalkylene ether repeating units, may be present.In the context of this disclosure, the term “poly(trimethyleneether)glycol” encompasses PO3G made from substantially pure1,3-propanediol, as well as those oligomers and polymers (includingthose described below) containing up to about 50% by weight ofcomonomers.

PO3G can be made via a number of processes known in the art, such asprocesses disclosed in U.S. Pat. No. 7,161,045 and U.S. Pat. No.7,164,046.

As indicated above, PO3G may contain lesser amounts of otherpolyalkylene ether repeating units in addition to the trimethylene etherunits. The monomers for use in preparing poly(trimethylene ether)glycolcan, therefore, contain up to 50% by weight (preferably about 20 wt % orless, more preferably about 10 wt % or less, and still more preferablyabout 2 wt % or less), of comonomer polyols in addition to the1,3-propanediol reactant. Comonomer polyols that are suitable for use inthe process for making the PO3G include aliphatic diols, for example,ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol,3,3,4,4,5,5-hexafluoro-1,5-pentanediol,2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol;cycloaliphatic diols, for example, 1,4-cyclohexanediol,1,4-cyclohexanedimethanol and isosorbide; and polyhydroxy compounds, forexample, glycerol, trimethylolpropane, and pentaerythritol. A preferredgroup of comonomer diols is selected from the group consisting ofethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol,C₆-C₁₀ diols (such as 1,6-hexanediol, 1,8-octanediol and1,10-decanediol) and isosorbide, and mixtures thereof. A particularlypreferred diol other than 1,3-propanediol is ethylene glycol, and C₆-C₁₀diols can be particularly useful as well.

One preferred PO3G that contains comonomer is poly(trimethylene-ethyleneether)glycol. Preferred poly(trimethylene-ethylene ether)glycols areprepared by acid catalyzed polycondensation of from 50 to about 99 mole% (preferably from about 60 to about 98 mole %, and more preferably fromabout 70 to about 98 mole %) 1,3-propanediol and up to 50 to about 1mole % (preferably from about 40 to about 2 mole %, and more preferablyfrom about 30 to about 2 mole %) ethylene glycol.

Preferably the PO3G has an Mn (number average molecular weight) of atleast about 250, more preferably at least about 500, and still morepreferably at least about 1000. The Mn is preferably less than about10000, more preferably less than about 5000, and still more preferablyless than about 2500. Blends of PO3Gs can also be used. For example, thePO3G can comprise a blend of a higher and a lower molecular weight PO3G,preferably wherein the higher molecular weight PO3G has a number averagemolecular weight of from about 1000 to about 5000, and the lowermolecular weight PO3G has a number average molecular weight of fromabout 200 to about 950. The Mn of the blended PO3G will preferably stillbe in the ranges mentioned above.

Preferred PO3G is polydisperse, having a polydispersity (i.e. Mw/Mn) ofpreferably from about 1.0 to about 2.2, more preferably from about 1.2to about 2.2, and still more preferably from about 1.5 to about 2.1. Thepolydispersity can be adjusted by using blends of PO3G.

The functionalized polyamines disclosed herein are suitable for use in avariety of applications including as chain extenders for polyurethaneurea polymers, curing agents for epoxy resins, polyurethane coatings,components for making polyamides, initiators for the preparation ofpolyols, and health care product additives.

EXAMPLES

DSC measurements were performed on a TA Instruments Q2000. Samples wereallowed to undergo heating, cooling, and re-heating cycle from −90° C.to 100° C. at a rate of 10° C./min under nitrogen. TGA measurements wereperformed on a TA Instruments Q500. Samples were heated from RT to 500°C. at a rate of 5° C./min under nitrogen.

Example 1

Poly(trimethylene ether)glycol (Compound 1) (50.0 g, M_(n,NMR)=652g/mol, M_(n,SEC)=699 g/mol, PDI=1.44), was dissolved in toluene (150 mL)and DMF (0.237 mL). The solution mixture was cooled down to 0° C. Tothis was added toluene (50 mL) solution of thionyl chloride (73.1 g,44.8 mL) slowly over 1.5 hour. The mixture was allowed to stir at 0° C.for 1 hour, at ambient temperature (approximately 25° C.) for 30 min,and at 85° C. for 3 hours. Excess thionyl chloride was removed undervacuum. The crude was re-suspended in methylene chloride (150 mL) withneutral alumina, filtered, and concentrated to obtain Compound 2 (49.0g): ¹H NMR (CDCl₃, 500 MHz) δ 3.63 (t, J=6.5 Hz, 4H), 3.54 (t, J=6.1 Hz,4H), 3.48 (m, ˜34H), 2.01 (quint, J=6.2 Hz, 4H), 1.82 (m, ˜17H); ¹³C NMR(CDCl₃, 500 MHz) δ 68.62, 68.53, 68.37, 67.80, 42.60, 33.44, 30.78,30.73; IR: 2804-2949, 1489, 1452, 1375, 1300, 1256, 1117, 927, 660 cm⁻¹;SEC: M_(n)=684 g/mol, PDI=1.41; IV: 0.043 mL/g; T_(g): −86° C.; T_(c):−50° C.; T_(m): −7, 4° C.; T₅₀: 204° C. (temperature of 50% weight lossbased on TGA data). The DSC measurements were performed on a TAInstruments Q2000. Samples were allowed to undergo heating, cooling, andre-heating cycle from −90° C. to 100° C. at a rate of 10° C./min undernitrogen. TGA measurements were performed on a TA Instruments Q500.Samples were heated from RT to 500° C. at a rate of 5° C./min undernitrogen.

Compound 2 (40.0 g) was dissolved in DMF (200 mL) followed by additionof sodium azide (30.2 g). The reaction mixture was heated to 100° C. for4 hours under nitrogen. The reaction mixture was filtered and thefiltrate was concentrated to obtain Compound 3 in quantitative yield: ¹HNMR (DMSO-d₆, 500 MHz) δ 3.39 (m, ˜42H), 1.75 (quint, J=6.5 Hz, 4H),1.69 (m, ˜17H); ¹³C NMR (DMSO-d₆, 500 MHz) δ 67.52, 67.43, 67.39, 67.27,48.34, 30.34, 29.98, 28.97; IR: 3518 (DMF), 2803-2949, 2096, 2063 (DMF),1665 (DMF), 1489, 1446, 1373, 1280, 1115, 941, 779 cm⁻¹; SEC: M_(n)=701g/mol, PDI=1.38.

To a pressure vessel (100 mL) was added an ethanol (10 mL) solution ofCompound 3 (4.0 g), followed by the addition of palladium (10 wt. % onactivated carbon, 0.24 g). The solution mixture was place under hydrogen(20 psi) at ambient temperature (approximately 25° C.) overnight. Thereaction mixture was filtered and concentrated to provide Compound 4: ¹HNMR (DMSO-d₆, 500 MHz) δ 3.38 (m, ˜42H), 2.57 (t, J=6.8 Hz, 4H), 1.69(m, ˜20H), 1.55 (t, J=6.7 Hz, 4H); IR: 3580 (DMF), 3392, 3318,2804-2947, 2056 (DMF), 1682 (DMF), 1627, 1489, 1445, 1371, 1328, 1256,1115, 933, 771 cm⁻¹; SEC: M_(n)=701 g/mol, PDI=1.38.

Example 2

Poly(trimethylene ether)glycol (Compound 1) (80.0 g) was combined withtriethylamine (50.8 mL) and dichloromethane (DCM) (800 mL). The reactionmixture was cooled down to −10° C. with stirring under nitrogen. To thiswas added DCM (400 mL) solution of mesyl chloride (23.7 mL) slowly.After 40 min, the reaction mixture was filtered and the filtrate waswashed with dilute HCl (0.5 M). The combined organic layer was washedwith sodium bicarbonate solution (8 wt. %), DI water, dried with MgSO₄,filtered, and concentrated to provide Compound 5 (90.9 g): ¹H NMR(CDCl₃, 500 MHz) δ 4.33 (t, J=6.3 Hz, 4H), 3.52 (t, J=5.9 Hz, 4H), 3.48(m, ˜36H), 3.00 (s, 6H), 2.00 (quint, J=6.1 Hz, 4H), 1.82 (m, ˜18H); ¹³CNMR (CDCl₃, 500 MHz) δ 68.60, 68.28, 68.24, 68.06, 66.46, 37.60, 30.52,30.43, 29.94; IR: 2810-2957, 1487, 1445, 1358, 1265, 1177, 1115, 980,951, 845, 530 cm⁻¹.

Compound 5 (10.0 g) was dissolved in methanol (40 mL) followed byaddition of sodium azide (4.83 g). The reaction mixture was heated to50-55° C. for 36 hours under nitrogen. The reaction mixture was filteredand the filtrate was concentrated to obtain Compound 3 (9.2 g): ¹H NMR(CDCl₃, 500 MHz) δ 3.48 (m, ˜42H), 3.38 (t, J=6.7 Hz, 4H), 1.82 (m,˜23H); ¹³C NMR (CDCl₃, 500 MHz) δ 68.08, 68.00, 67.83, 67.47, 30.22,30.16, 29.62; IR: 2804-2949, 2099, 1486, 1439, 1373, 1304, 1265, 1117,943, 777 cm⁻¹; SEC: M_(n)=675 g/mol, PDI=1.44; T_(g): <−100° C.; T_(c):−63° C.; T_(m): −9, 5° C.; T₅₀: 354° C.

Compound 3 was converted to Compound 4 under similar condition describedin Example 1: ¹H NMR (CDCl₃, 500 MHz) δ 3.48 (m, ˜42H), 2.79 (t, J=6.8Hz, 4H), 1.82 (m, ˜19H), 1.71 (quint, J=1.71 Hz, 4H), 1.19 (br s, 4H);¹³C NMR (CDCl₃, 500 MHz) δ 69.42, 68.29, 67.96, 39.82, 33.73, 30.36,30.22; IR: 3397, 3337, 2806-2947, 1628, 1487, 1485, 1444, 1373, 1117,934, 835 cm⁻¹; T_(g): −83° C.; T_(c): −48° C.; T_(m): −5, 7, 10° C.;T₅₀: 345° C.

Example 3

Compound 2 is dissolved in a mixture of aqueous ammonia/isopropanol. Thereaction mixture is placed in a pressure vessel and heated to 60° C.After the reaction is complete, solvents and reagents are removed undervacuum. Compound 4 is prepared in its free amine form after treatmentwith ion exchange resin or by dialysis.

Example 4

Compound 2 and anhydrous ammonia are combined in a sealed pressurevessel. The reaction mixture is heated to 60° C. The crude material isdissolved in a mixture of water and isopropanol followed by treatmentwith ion exchange resin or by dialysis to provide Compound 4 in its freeamine form.

Example 5

Compound 5 is dissolved in a mixture of aqueous ammonia/isopropanol. Thereaction mixture is placed in a pressure vessel and heated to 60° C.After the reaction is complete, solvents and reagents are removed undervacuum. Compound 4 is prepared in its free amine form after treatmentwith ion exchange resin or by dialysis.

Example 6

Compound 5 and anhydrous ammonia are combined in a sealed pressurevessel. The reaction mixture is heated to 60° C. The crude material isdissolved in a mixture of water and isopropanol followed by treatmentwith ion exchange resin or by dialysis to provide Compound 4 in its freeamine form.

Example 7

Compound 1 is combined with catalytic amount of sodium hydroxide andradical inhibitor monomethyl ether hydroquinone (MEHQ) (10-100 ppm) in aappropriate solvent such as toluene, dioxane, THF. Acrylonitrile (2-10equiv. to the OH groups in Compound 1) is then added slowly to thesolution mixture with proper cooling at 0-20° C. to avoid over heat dueto the exothermic reaction. The reaction mixture is heated at 30-80° C.to complete conversion. The reaction mixture is then cooled to roomtemperature and quenched by dropwise addition of acetic acid. Solvent aswell as the unreacted acrylonitrile are evaporated under vacuum and thereaction mixture was partitioned between methylene chloride and water.The organic layer is water washed, dried, and concentrated to provideCompound 6. Crude Compound 6 is optionally further purified beforereduction.

Compound 6 is dissolved in methanol saturated with ammonia, followed bythe addition of catalytic amounts of Raney nickel. The solution mixtureis placed under hydrogen (150 psi) at RT overnight. Catalyst is filteredand the reaction mixture is concentrated to provide Compound 4.

1. A poly(trimethylene ether)diamine of the formula

wherein n is 4 to
 170. 2. The poly(trimethylene ether)diamine of claim1, wherein the poly(trimethylene ether)amine is formed from apoly(trimethylene ether)glycol obtained from the polycondensation ofbiologically-derived 1,3-propane diol.
 3. A process for making apoly(trimethylene ether)diamine of the formula

comprising: a) converting the chain-end hydroxyl groups ofpoly(trimethylene ether)glycol of the formula

to better leaving groups to form a compound of formula

where Z is selected from the group consisting of mesylate (—OMs),tosylate (—OTs), nosylate (—ONs), brosylate (—OBs), triflate (—OTf),nonaflate, tresylate and iodide (—I). b) combining the compound of step(a) with anhydrous ammonia, or a mixture of aqueous ammonia and asolvent, under a pressure of about 15 to 500 psi at a temperature of 25to 150° C. to form a poly(trimethylene ether)diamine of the formula

wherein n is 4 to
 170. 4. A process for making a poly(trimethyleneether)diamine of the formula

comprising: a) converting the chain-end hydroxyl groups ofpoly(trimethylene ether)glycol of the formula

to nitrile groups to form a nitrile-terminated poly(trimethylene ether)of formula

b) reducing the nitrile-terminated poly(trimethylene ether) in thepresence of hydrogen and catalyst at a temperature of 50 to 250° C.under pressure of 80 to 4000 psi to form a poly(trimethyleneether)diamine of the formula

wherein n is 4 to
 170. 5. The process of claim 3 or 4, wherein thepoly(trimethylene ether)glycol is biologically derived.
 6. The processof claim 5, further comprising purifying the poly(trimethyleneether)diamine.
 7. The process of claim 6, wherein the purifyingcomprises a process selected from the group consisting of: (a) treatingthe poly(trimethylene ether)diamine by washing and extracting withsolvents; (b) treating the poly(trimethylene ether)diamine by passingthrough one or more ion exchange columns; (c) treating thepoly(trimethylene ether)diamine by dialysis through membranes againstsolvent; (d) treating the poly(trimethylene ether)diamine with activatedcarbon; (e) treating the poly(trimethylene ether)diamine using acombination of (a) to (d).